EP0448177B1 - Herstellung von Polyketonen - Google Patents
Herstellung von Polyketonen Download PDFInfo
- Publication number
- EP0448177B1 EP0448177B1 EP91200625A EP91200625A EP0448177B1 EP 0448177 B1 EP0448177 B1 EP 0448177B1 EP 91200625 A EP91200625 A EP 91200625A EP 91200625 A EP91200625 A EP 91200625A EP 0448177 B1 EP0448177 B1 EP 0448177B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- addition rate
- catalyst
- diluent
- period
- running
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2/00—Addition polymers of aldehydes or cyclic oligomers thereof or of ketones; Addition copolymers thereof with less than 50 molar percent of other substances
- C08G2/18—Copolymerisation of aldehydes or ketones
- C08G2/26—Copolymerisation of aldehydes or ketones with compounds containing carbon-to-carbon unsaturation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G67/00—Macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing oxygen or oxygen and carbon, not provided for in groups C08G2/00 - C08G65/00
- C08G67/02—Copolymers of carbon monoxide and aliphatic unsaturated compounds
Definitions
- the invention relates to a process for the preparation of polyketone polymers, i.e. polymers of carbon monoxide with one or more olefinically unsaturated compounds.
- Linear polymers of carbon monoxide with one or more olefinically unsaturated compounds in which polymers the units originating from carbon monoxide on the one hand and the units originating from the olefinically unsaturated compound(s) used on the other hand occur in a substantially alternating arrangement, can be prepared by contacting the monomers at elevated temperature and pressure, in the presence of a diluent in which the polymers are insoluble or virtually insoluble, with a suitable catalyst.
- the preparation of the polymers can, in principle, be carried out in either of two manners, viz. batchwise or continuously.
- Batchwise preparation of the polymers is carried out by introducing catalyst into a reactor containing diluent and monomers and which is at the desired temperature and pressure. As polymerization proceeds, the pressure drops, the concentration of the polymers in the diluent increases and the viscosity of the suspension rises. Polymerization is continued until the viscosity of the suspension has reached such a high value that continuing the process further would create difficulties, e.g. in connection with heat removal. In principle, the only parameter which remains constant in batchwise polymer preparation is the temperature. A variant of batchwise polymer preparation is semi-batchwise preparation in which besides the temperature also the pressure is kept constant by adding monomers to the reactor during the polymerization.
- a diluent, monomers and catalyst are continuously added to a reactor containing monomers and a certain volume of the diluent and which is at the desired temperature and pressure, and a polymer suspension is continuously withdrawn from it.
- the temperature, the pressure and the liquid volume in the reactor are kept substantially constant.
- a stationary state is reached which is characterized, inter alia, by the suspension withdrawn from the reactor having a substantially constant polymer content and the polymers contained therein having constant properties.
- a continuous process is greatly to be preferred to bachwise or semi-batchwise production for the following reasons.
- the continuous process gives a higher polymer output because the production does not, as in batchwise preparation, have to be frequently interrupted for charging and discharging the reactor.
- continuous operation in contrast with bachwise production, is characterized by all the reaction parameters remaining substantially constant, a continuous process is easier to regulate and is more suitable for automation.
- the continuous process produces polymers which exhibit less variation in properties and therefore have a more constant quality than those obtained from batchwise production.
- the bulk density This plays an important role both in the preparation and in the treatment, storage, transport and processing of the polymers.
- the rule of thumb is that the maximum permissible suspension concentration, expressed in (kg polymer/kg suspension) x 100, is about one-tenth of the bulk density expressed in kg/m3. This means that, in the preparation of a polymer with a bulk density of 100 kg/m3, the maximum suspension concentration is about 10%, whereas in the preparation of a polymer with a bulk density of 500 kg/m3, the maximum suspension concentration is about 50%.
- quintupling the bulk density offers the possibility of preparing about five times the quantity of polymer in the same reactor volume.
- the quantity of adhering liquid is largely determined by the polymer bulk density.
- a polymer with a bulk density of 100 kg/m3 binds approx. 5 kg diluent or washing liquid per kg, whereas that quantity is only about 0.25 kg for a polymer with a bulk density of 500 kg/m3.
- This is naturally of great importance on account of the quantity of liquid that must be used in washing the polymers and must be removed when the polymers are dried.
- transport and storage are concerned, the rule is that the higher the polymers' bulk density, the more attractive the flow behaviour they will have and the less space they will occupy.
- polymers with low bulk density cause problems in the processing apparatus.
- Polymers with low bulk density must often be compacted, for example by extrusion, in order to make them suitable for further processing in the equipment usual for that purpose.
- the higher the polymers' bulk density the less need there will be for prior treatment of the material, which will be suitable for further processing as it is.
- the stationary period is preceded by a running-in period.
- both the polymer content of the suspension and the bulk density of the prepared polymers increase.
- the running-in procedure is carried out by adding the feed streams to a reactor containing monomers and diluent and which is at the temperature and pressure chosen for the stationary period.
- a catalyst addition rate should be employed at the start of the running-in period which is smaller than k and/or a diluent addition rate which is greater than v and the catalyst addition rate should be increased and the diluent addition rate should be reduced during the running-in period such that at the end of the running-in period they have the values k and v respectively.
- the present patent application therefore relates to a process for the preparation of polyketone polymers
- k and v are preferably chosen such that during the stationary period the suspension concentration is at least 12.5% and the average residence time of the suspension in the reactor is 2-30 hours.
- both the catalyst addition rate and the diluent addition rate can be changed during the running-in period. Preferably, these changes are carried out stepwise. There is further preference for changing only one of the addition rates during the running-in period, in particular only the catalyst addition rate.
- a catalyst addition rate is preferably chosen at the beginning of the running-in period that amounts to 15-25% of the final value of k.
- the catalyst addition rate is raised during each stepwise change by an amount corresponding to 15 to 35% of the final value of k.
- the time interval between the successive increases of the catalyst addition rate preferably corresponds to 1-3 times the average residence time of the suspension in the reactor.
- a catalyst which is capable of, starting from a mixture of carbon monoxide and one or more olefinically unsaturated compounds, catalyzing the formation of the linear alternating polymers mentioned hereinbefore.
- Catalysts that are suitable for the present purpose are, inter alia, those which include a Group VIII metal.
- Group VIII metals are understood to be the noble metals ruthenium, rhodium, palladium, osmium, iridium and platinum, as well as the iron group metals iron, cobalt and nickel.
- Preference is given to catalysts which include palladium, nickel or cobalt as Group VIII metal. Special preference is given to palladium as the Group VIII metal.
- the catalysts that are used in the process of the invention comprise a Group VIII metal
- they are incorporated in the catalyst preferably in the form of a salt of a carboxylic acid, in particular in the form of an acetate.
- the catalysts preferably include a dentate ligand in which at least two dentate groups occur, selected from phosphorus-containing, nitrogen-containing and sulphur-containing dentate groups, whereby the dentate ligand can complex with the Group VIII metal.
- dentate ligands containing more than two dentate groups are also eligible for this purpose, such as the tetradentate ligand 1,8-bis[bis(2-methoxyphenyl)phosphino]-2,7-bis[bis(2-methoxyphenyl)phosphinomethyl]octane
- bidentate ligands are preferred.
- X represents an organic bridging group containing three or four atoms in the bridge, at least two of which are carbon atoms, such as 2,2'-bipyridine and 1,10-phenanthroline.
- R1S-R-SR1 When use is made of a sulphur bidentate ligand, it is preferred to use compounds of the general formula R1S-R-SR1, wherein R1 represents an optionally polar-substituted hydrocarbon group and R is a bivalent organic bridging group which has at least two carbon atoms in the bridge, such as 1,2-bis(ethylthio)ethane and cis-1,2-bis(benzylthio)ethene.
- R1 represents an optionally polar-substituted hydrocarbon group
- R is a bivalent organic bridging group which has at least two carbon atoms in the bridge, such as 1,2-bis(ethylthio)ethane and cis-1,2-bis(benzylthio)ethene.
- R1 represents an optionally polar-substituted hydrocarbon group
- R is a bivalent organic bridging group which has at least two carbon atoms in the bridge, such as 1,2-
- phosphorus bidentate ligands in which R1 represents an aromatic hydrocarbon group having at least one alkoxy substituent in the ortho position relative to the phosphorus atom to which it is bound.
- a compound which is very suitable for the present purpose is 1,3-bis[bis(2-methoxyphenyl)phosphino]propane.
- the applied quantity is preferably 0.5-100 and in particular 1-50 mol per mol of Group VIII metal.
- the applied quantity is preferably 0.5-2 and in particular 0.75-1.5 mol per mol of Group VIII metal.
- the catalysts preferably include an anion of an acid with a pKa of less than 4 and in particular an anion of an acid with a pKa of less than 2.
- the anion can be introduced into the catalyst either in the form of a compound from which the desired anion splits off or in the form of a mixture of compounds from which the desired anion is formed by interaction.
- Both mineral acids and organic acids are eligible as acids with a pka of less than 4. Examples of suitable mineral acids are sulphuric acid and perchloric acid. Examples of suitable organic acids are sulphonic acids such as para-toluenesulphonic acid and halogen carboxylic acids such as trifluoroacetic acid.
- the anion can be incorporated in the catalyst in the form of a carboxylic acid or in the form of a derivative thereof such as an alkyl or aryl ester, an amide, an imide, an anhydride, an ortho-ester, a lactone, a lactam or an alkylidene dicarboxylate.
- the anion is preferably present in the catalysts in a quantity of 1-100 and in particular 2-50 mol per mol of Group VIII metal.
- the anion of an acid with a pKa of less than 4 can also be present in the catalyst because, for example, palladium trifluoroacetate or palladium para-tosylate was used as Group VIII metal compound.
- a 1,4-quinone may be additionally incorporated therein.
- 1,4-benzoquinone and 1,4-naphthoquinone are very suitable.
- the quantity of 1,4-quinone used preferably amounts to 5-5,000 and in particular 10-1,000 mol per mol Group VIII metal.
- Olefinically unsaturated compounds that can be polymerized with carbon monoxide by using the process of the invention can be compounds consisting exclusively of carbon and hydrogen as well as compounds which contain, in addition to carbon and hydrogen, one or more hetero-atoms.
- the process of the invention is preferably applied for the preparation of polymers of carbon monoxide with one or more olefinically unsaturated hydrocarbons.
- suitable hydrocarbon monomers are ethene, propene, butene-1, hexene-1, octene-1, styrene, cyclopentene, norbornene and dicyclopentadiene.
- the process of the invention is in particular very suitable for application in the preparation of copolymers of carbon monoxide with ethene and for the preparation of terpolymers of carbon monoxide with ethene and an ⁇ -olefin, in particular propene.
- the quantity of catalyst composition employed in the process of the invention may vary within wide limits.
- a quantity of catalyst composition is used which comprises 10 ⁇ 7-10 ⁇ 3 and in particular 10 ⁇ 6-10 ⁇ 4 mol of Group VIII metal per mol of olefinically unsaturated compound to be polymerized.
- the contacting of the monomers with the catalyst is, in the process of the invention, carried out in the presence of a diluent in which the polymers are insoluble or virtually insoluble.
- a diluent in which the polymers are insoluble or virtually insoluble.
- Very suitable for this purpose are lower aliphatic alcohols and in particular methanol.
- the process of the invention is preferably carried out in two or more reactors connected in series. If reactors connected in series are used, preferably not more than three reactors are used.
- the process of the invention is preferably carried out at a temperature of 25-150°C and a pressure of 2-150 bar and in particular at a temperature of 30-130°C and a pressure of 5-100 bar.
- the molar ratio of olefinically unsaturated compounds relative to carbon monoxide is preferably 10:1-1:10 and in particular 5:1-1:5.
- Solution 1 contained 1000 mg palladium acetate per litre acetone, 2491 mg 1,3-bis[bis(2-methoxyphenyl)phosphino]propane and 1067 mg trifluoroacetic acid.
- Solution 2 contained 3000 mg trifluoroacetic acid per litre acetone.
- the suspension mass in the reactor was 70 kg.
- Reactor pressure 45 bar
- Reactor temperature 80°C
- Gas phase composition 30 mol % carbon monoxide 45 mol % ethene 25 mol % propene
- examples 3 and 4 are according to the invention.
- carbon monoxide/ethene/propene terpolymers were prepared in a continuous manner using a starting-up procedure in which either the catalyst addition rate was raised (example 3) or the diluent addition rate was reduced (example 4) to the values chosen for the stationary period.
- polymers could be prepared during the stationary period of the continuous process at suspension concentrations of 14 and 17.9%, the polymers having bulk densities of 200 and 260 kg/m3 respectively.
- Examples 1 and 2 fall outside the scope of the invention and are only included in the patent application for comparison.
- carbon monoxide/ethene copolymers were prepared in a continuous manner using a starting-up procedure in which both the catalyst addition rate and the diluent addition rate corresponded with the values chosen for the stationary period. In this way, polymers with a bulk density of only 70 kg/m3 could be prepared during the stationary period of the continuous process at a suspension concentration of just 4%.
- example 2 an attempt was made to improve the results of example 1 by using a considerably higher catalyst addition rate.
- the experiment described in this example had, however, to be broken off in connection with the extremely high viscosity of the suspension before the stationary state was reached.
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyethers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Claims (10)
- Verfahren zur Herstellung von Polyketonen, dadurch gekennzeichnet, daßa) man durch Kontaktieren der Monomere bei erhöhter Temperatur und erhöhtem Druck in Gegenwart eines Verdünnungsmittels, in dem die Polymere unlöslich oder praktisch unlöslich sind, mit einem geeigneten Katalysator lineare Polymere aus Kohlenmonoxid und einer oder mehreren olefinisch ungesättigten Verbindungen herstellt, wobei in den Polymeren die vom Kohlenmonoxid stammenden Einheiten und die von der/den olefinisch ungesättigten Verbindung(en) stammenden Einheiten in einer weitgehend alternierenden Reihenfolge vorkommen,b) wobei man die Herstellung kontinuierlich durchführt und die Katalysatorzusatzrate während der stationären Phase einen Wert k und die Verdünnungsmittelzusatzrate einen Wert v hat,c) wobei man bei der Einlaufphase so verfährt, daß man die Einspeisematerialien einem Reaktor zusetzt, der Monomere und Verdünnungsmittel enthält und der sich bei der/dem für die stationäre Phase gewählten Temperatur und Druck befindet, undd) wobei man zu Beginn der Einlaufphase eine Katalysatorzusatzrate, die niedriger als k ist und/oder eine Verdünnungsmittelzusatzrate, die höher als v ist, verwendet unde) wobei man während der Einlaufphase die Katalysatorzusatzrate erhöht und/oder die Verdünnungsmittelzusatzrate verringert, wobei man dieses so ausführt, daß sie am Ende der Einlaufphase im wesentlichen jeweils den Wert k und v haben.
- Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man k und v so auswählt, daß die Suspensionskonzentration während der stationären Phase mindestens 12,5% und die mittlere Verweilzeit der Suspension im Reaktor 2-30 Stunde beträgt.
- Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß man die Erhöhung der Katalysatorzusatzrate und/oder die Verringerung der Verdünnungsmittelzusatzrate schrittweise ausführt.
- Verfahren nach einem der Ansprüche 1-3, dadurch gekennzeichnet, daß man während der Einlaufphase nur die Katalysatorzusatzrate verändert, während man die Verdünnungsmittelzusatzrate konstant bei dem Wert v hält.
- Verfahren nach Anspruch 4, dadurch gekennzeichnet, daß man bei der Ausführung des Anfahrens unter Anwendung einer schrittweisen Erhöhung der Katalysatorzusatzrate so vorgeht, daß man zu Beginn der Einlaufphase eine Katalysatorzusatzrate wählt, die 15-25% des endgültigen Wertes k beträgt.
- Verfahren nach Anspruch 5, dadurch gekennzeichnet, daß man die Katalysatorzusatzrate bei jeder schrittweisen Veränderung um eine 15 bis 35% des endgültigen Wertes für k entsprechende Menge erhöht.
- Verfahren nach Anspruch 5 oder 6, dadurch gekennzeichnet, daß die Zeit zwischen aufeinanderfolgenden Erhöhungen der Katalysatorzusatzrate bis zu dreimal so lang ist wie die mittlere Verweilzeit der Suspension im Reaktor.
- Verfahren nach einem der Ansprüche 1-7, dadurch gekennzeichnet, daß der Katalysator ein Metall der Gruppe VIII und einen zähnigen Liganden enthält, in dem mindestens zwei zähnige, aus phosphor-, stickstoff- und schwefelhaltigen zähnigen Gruppen ausgewählte Gruppen vorliegen, wodurch der zähnige Ligand mit dem Metall der Gruppe VIII einen Komplex bilden kann.
- Verfahren nach Anspruch 8, dadurch gekennzeichnet, daß der Katalysator auch ein Anion einer Säure mit einem pKs-Wert kleiner 4 enthält.
- Verfahren nach einem der Ansprüche 1-9, dadurch gekennzeichnet, daß man als Verdünnungsmittel einen niederen aliphatischen Alkohol wie z.B. Methanol einsetzt.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
NL9000677 | 1990-03-22 | ||
NL9000677 | 1990-03-22 |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0448177A2 EP0448177A2 (de) | 1991-09-25 |
EP0448177A3 EP0448177A3 (en) | 1992-03-25 |
EP0448177B1 true EP0448177B1 (de) | 1995-12-27 |
Family
ID=19856796
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP91200625A Expired - Lifetime EP0448177B1 (de) | 1990-03-22 | 1991-03-20 | Herstellung von Polyketonen |
Country Status (19)
Country | Link |
---|---|
US (1) | US5122591A (de) |
EP (1) | EP0448177B1 (de) |
JP (1) | JPH04222830A (de) |
KR (1) | KR0178527B1 (de) |
CN (1) | CN1031136C (de) |
AR (1) | AR247407A1 (de) |
AU (1) | AU637888B2 (de) |
BR (1) | BR9101083A (de) |
CA (1) | CA2038654A1 (de) |
CZ (1) | CZ280546B6 (de) |
DE (1) | DE69115737T2 (de) |
ES (1) | ES2081421T3 (de) |
FI (1) | FI101971B (de) |
HU (1) | HU210081B (de) |
MY (1) | MY104758A (de) |
PL (1) | PL167050B1 (de) |
RU (1) | RU2021288C1 (de) |
TR (1) | TR25073A (de) |
ZA (1) | ZA912061B (de) |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0605062B1 (de) * | 1992-12-31 | 1999-07-14 | Shell Internationale Researchmaatschappij B.V. | Herstellung von Copolymeren aus Kohlenmonoxid und ethylenisch ungesättigten Verbindungen |
US5352766A (en) * | 1992-12-31 | 1994-10-04 | Shell Oil Company | Preparation of copolymers |
AU683515B2 (en) * | 1993-11-19 | 1997-11-13 | Shell Internationale Research Maatschappij B.V. | Polyketone polymer composition |
EP1049092B1 (de) | 1999-04-28 | 2007-03-07 | Sharp Kabushiki Kaisha | Plattenkassette |
IT1312337B1 (it) | 1999-05-07 | 2002-04-15 | Agip Petroli | Composizione catalitica per l'upgrading di idrocarburi aventi punti di ebollizione nell'intervallo della nafta |
KR100652087B1 (ko) * | 2004-11-24 | 2006-12-01 | 주식회사 효성 | 폴리케톤의 제조방법 |
KR100652072B1 (ko) * | 2004-11-24 | 2006-12-01 | 주식회사 효성 | 폴리케톤의 제조방법 |
KR100595562B1 (ko) * | 2004-11-24 | 2006-07-03 | 주식회사 효성 | 폴리케톤의 제조방법 |
KR100643673B1 (ko) * | 2004-11-30 | 2006-11-10 | 주식회사 효성 | 폴리케톤의 제조방법 |
CN115536836A (zh) * | 2022-11-02 | 2022-12-30 | 黄河三角洲京博化工研究院有限公司 | 一种高堆积密度聚酮的制备方法 |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3694412A (en) * | 1971-03-04 | 1972-09-26 | Shell Oil Co | Process for preparing interpolymers of carbon monoxide in the presence of aryl phosphine-palladium halide complex |
ATE49010T1 (de) * | 1983-04-06 | 1990-01-15 | Shell Int Research | Verfahren zur herstellung von polyketonen. |
NL8403035A (nl) * | 1984-10-05 | 1986-05-01 | Shell Int Research | Werkwijze ter bereiding van polyketonen. |
IN166314B (de) * | 1985-08-29 | 1990-04-07 | Shell Int Research | |
NL8602164A (nl) * | 1986-08-26 | 1988-03-16 | Shell Int Research | Katalysatorcomposities. |
IN171627B (de) * | 1986-08-26 | 1992-11-28 | Shell Int Research | |
AU612173B2 (en) * | 1987-08-28 | 1991-07-04 | Shell Internationale Research Maatschappij B.V. | Preparation of olefin/CO copolymers |
CA1338576C (en) * | 1988-02-10 | 1996-09-03 | Maarten Marinus Geuze | Polyketone polymer preparation |
US5021547A (en) * | 1989-08-07 | 1991-06-04 | Shell Oil Company | Continuous polymerization of Co/olefin in plurality of reactors in series |
-
1991
- 1991-03-13 US US07/668,848 patent/US5122591A/en not_active Expired - Fee Related
- 1991-03-19 KR KR1019910004340A patent/KR0178527B1/ko not_active IP Right Cessation
- 1991-03-20 CA CA002038654A patent/CA2038654A1/en not_active Abandoned
- 1991-03-20 CN CN91101711A patent/CN1031136C/zh not_active Expired - Fee Related
- 1991-03-20 PL PL91289509A patent/PL167050B1/pl unknown
- 1991-03-20 BR BR919101083A patent/BR9101083A/pt not_active IP Right Cessation
- 1991-03-20 ES ES91200625T patent/ES2081421T3/es not_active Expired - Lifetime
- 1991-03-20 JP JP3057169A patent/JPH04222830A/ja active Pending
- 1991-03-20 AR AR91319258A patent/AR247407A1/es active
- 1991-03-20 EP EP91200625A patent/EP0448177B1/de not_active Expired - Lifetime
- 1991-03-20 CZ CS91751A patent/CZ280546B6/cs not_active IP Right Cessation
- 1991-03-20 ZA ZA912061A patent/ZA912061B/xx unknown
- 1991-03-20 MY MYPI91000461A patent/MY104758A/en unknown
- 1991-03-20 AU AU73698/91A patent/AU637888B2/en not_active Ceased
- 1991-03-20 FI FI911357A patent/FI101971B/fi active
- 1991-03-20 DE DE69115737T patent/DE69115737T2/de not_active Expired - Fee Related
- 1991-03-20 RU SU914894989A patent/RU2021288C1/ru active
- 1991-03-20 HU HU91933A patent/HU210081B/hu not_active IP Right Cessation
- 1991-04-20 TR TR91/0288A patent/TR25073A/xx unknown
Also Published As
Publication number | Publication date |
---|---|
EP0448177A3 (en) | 1992-03-25 |
HU910933D0 (en) | 1991-10-28 |
FI101971B1 (fi) | 1998-09-30 |
PL289509A1 (en) | 1991-12-02 |
MY104758A (en) | 1994-05-31 |
US5122591A (en) | 1992-06-16 |
BR9101083A (pt) | 1991-11-05 |
TR25073A (tr) | 1992-11-01 |
HUT57242A (en) | 1991-11-28 |
CA2038654A1 (en) | 1991-09-23 |
DE69115737T2 (de) | 1996-05-15 |
CN1031136C (zh) | 1996-02-28 |
FI911357A (fi) | 1991-09-23 |
JPH04222830A (ja) | 1992-08-12 |
KR910016795A (ko) | 1991-11-05 |
AU7369891A (en) | 1991-10-03 |
EP0448177A2 (de) | 1991-09-25 |
DE69115737D1 (de) | 1996-02-08 |
CZ280546B6 (cs) | 1996-02-14 |
FI911357A0 (fi) | 1991-03-20 |
RU2021288C1 (ru) | 1994-10-15 |
ZA912061B (en) | 1991-11-27 |
AR247407A1 (es) | 1994-12-29 |
FI101971B (fi) | 1998-09-30 |
ES2081421T3 (es) | 1996-03-16 |
AU637888B2 (en) | 1993-06-10 |
KR0178527B1 (ko) | 1999-05-15 |
CN1054990A (zh) | 1991-10-02 |
PL167050B1 (pl) | 1995-07-31 |
HU210081B (en) | 1995-02-28 |
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